Composition and method for controlling aerobacter aerogenes

ABSTRACT

The present invention relates to certain processes and compositions useful for inhibiting and/or controlling the growth of slime in water and, in particular, water employed for industrial purposes. Water employed in the manufacture of pulp paper and water employed in cooling water systems, as well as other industrial waters, provide environments which are conducive to slime formation. The novel compositions of the present invention are mixtures which show unexpected synergistic activity against microorganisms, including bacteria, fungi and algae, which produce slime in aqueous systems. The slime, of course, is objectionable from an operational and/or an aesthetic point of view. Specifically, the invention is directed to and the use of compositions comprising a combination of 3,3,4,4,tetrachlorotetrahydrothiophene-1,1-dioxide and anionic sulfonate surfactants (or mixtures thereof). The inventive compositions inhibit the growth of slime in water, or more specifically, possess biocidal activity against bacteria, fungi and/or algae. The anionic sulfonate surfactants contemplated for use in accordance with the present invention may be exemplified by: alkali metal linear alkylate sulfonate, wherein the alkylate contains from 10 to 18 carbon atoms; and alkali metal-N-lower alkyl-N-high alkenoyl taurate, wherein the lower alkyl contains from 1 to 4 carbon atoms and the alkenoyl contains from 16 to 20 carbon atoms.

United States Patent 1 Shema et al. I i

[ June 28, 1974 [5 COMPOSITION ANDMETHOD FOR CONTROLLING AEROBACTER AEROGENES [75] Inventors: Bernard F. Shema, Glenside; Robert H. Brink, Jr., Doylestown; Roger L. Justice, Warrninster, all of Pa.

[73] Assignee: Betz Laboratories,lnc., Trevose, Pa. [22] Filed: Mar. 23, 1972 [21] Appl. No.: 237,534

[52] US. Cl 424/275, 71/67, 162/190, 424/298, 424/303, 424/312 [51] Int. CL. A0111 9/02 [58] Field of Search 71/67; 424/275, 313

[ 56] References Cited UNITED STATES PATENTS 2,939,871 6/1960 Pyne et a1. 71/91 3,073,691 H1963 Bluestone et a1. 71/91 Primary Examiner-James 0. Thomas, Jr. Attorney, Agent, or FirmAlexander D. Ricci; Eugene F. Miller [57] ABSTRACT The present invention relates to certain processes and compositions useful for inhibiting and/or controlling the growth of slime in water and, in particular, water employed for industrial purposes. Water employed in the manufacture of pulp paper and water employed in cooling water systems, as well as other industrial waters, provide environments which are conducive to slime formation. The novel compositions of the present invention are mixtures which show unexpected synergistic activity against microorganisms, including bacteria, fungi and algae, which produce slime in aqueous systems. The slime, of course, is objectionable from an operational and/or an aesthetic point of view. Specifically, the invention is directed to and the use of compositions comprising a combination of 3,3,- 4,4,-tetrachlorotetrahydrothiophenel l -dioxide and anionic sulfonate surfactants (or mixtures thereof).

Theinventive compositions inhibit the growth of slime 24 Claims, No Drawings BACKGROUND OF THE INVENTION The formation of slime by microorganisms is a problem which attends many systems. For example, lagoons, lakes, ponds, pools and such systems as cooling water systems and pulp and paper mill systems all possess conditions which are conducive to the growth and reproduction of slime-forming microorganisms. In both once-through and recirculating cooling systems, for example, which employ large quantities of water as a cooling medium, the formation of slime by microorgan isms is an extensive and constant problem. 1

Airborne organisms are readily entrained in the water from cooling towers and find this warm medium an ideal environment for growth and multiplication. Aerobic and heliotropic organisms flourish on the tower proper while other organisms colonize and grow in such areas as the tower sump and the piping and passages of the cooling system. Such slime serves to deteriorate the tower structure in the case of wooden towers.

In addition, the deposition of slime on metal surfaces promotes corrosion. Furthermore, slime carried through the cooling system plugs and fouls lines, valves,

' strainers, etc. and deposits on heat exchange surfaces.

In the latter case, the impedance of heat transfer can i greatly reduce the efficiency of the cooling system.

In pulp and paper mill systems, slime formed by microorganisms is also frequently and, in fact, commonly encountered. Fouling or plugging by slime also occurs in the case of pulp and paper mill systems. Of greater significance, the slime becomes entrained in the paper produced to cause breakouts on the paper machines with consequent work stoppages and the loss of production time or unsightly-blemishes in the final product; this, of course, results in rejects and wasted output. The previously discussed problems have resulted in the extensive utilization of biocides in cooling water and pulp and paper mill systems. Materials which have enjoyed widespread use in such applications include chlorine, or organo-mercurials, chlorinated phenols, or-.

gano-bromines, and various organo-sulfur compounds. All of these compounds are generally useful for this purpose but each is attended by a variety of impediments. For example, chlorination is limited both by its specific toxicity for slime-forming organisms at economic levels and by the ability of chlorine to react which results in the expenditure of the chlorine before its full biocidal function may be achieved. Other biocides are attended by high costs, odor problems and hazards in respect to storage, use or handling which limit their utility. To date, no one compound or type of compound has achieved a clearly established predominance in respect to the applications discussed. Likewise, lagoons, ponds, lakes and even pools, either used for pleasure purposes or used for industrial purposes for the disposal and storage of industrial wastes, become during the warm weather besieged by slime due to microorganism growth and reproduction. In the case of the recreational areas, the problem of infection, odor, etc. is obvious. In the case of industrial storage or disposal of industrial materials, the microorganisms cause additional problems which must be eliminated prior to the materials use or the waste is treated for disposal.-

- LII It is the object of the present invention to provide compositions for controlling slime-forming microorganisms in aqueous systems, such as cooling water systems and pulp and paper mill systems, and for controlling slime formation or microorganism populations in aqueous bodies in general. Moreover, another object of the invention is the provision of methods for preserving materials and for controlling slime-forming microor ganisms in any agueous system which is conducive to the growth and reproduction of microorganisms, and, in particular, cooling water and paper and pulp mill systems. These methods employ a combination of 3,3,4,4- tetrachlorotetrahydrothiophene-l,l-dioxide and an anionic sulfonate surfactant (or mixtures thereof). The anionic sulfonate surfactant to be effective must possess the property of being capable of controlling the growth of bacteria, fungi and/or algae.

In thepractice of the invention, the combination is added to the particular material to be preserved or to the system being treated, for example, cooling water systems, paper and pulp mill systems, pools, ponds, la-

goons, lakes, etc., in a quantity adequate to control the GENERAL DESCRIPTION OF THE INVENTION As earlier stated, the inventive compositions comprise a combination of 3,3,4,4- tetrachlorotetrahydrothiophene-l ,l-dioxide and a particular anionic sulfonate surfactant (or mixtures thereof) with either compound being present in such a quantity as to impart a synergistic behavior for the purpose to the composition as a whole. Preferably, the compositions contain a percentage by weight ranging from about 5 to of the 3,3,4,4- tetrachlorotetrahydrothiophenel l -dioxide compoundand from about 5 to about 95% of the anionic sulfonate surfactant which may be exemplified by compounds such as alkali metal linear alkylate sulfonates where the alkyl branch contains from 10 to 18 carbon atoms. The alkali metal may be in fact sodium, potas sium and the equivalent ammonium. The anionic sulfonate may in fact be a mixture where the size of the'alkyl branch ranges from 10 to '18 with the preferable average size being about l2. The term alkylate as used in the above nomenclature refers basically to the reaction product of benzene or its homologues with a long chain olefin to produce an alkylated benzene such as dodecylbenzene. Other compounds can. be exemplified by the family ofv compounds generically described as the alkali metal or ammonium salt of an N-alkyl-N- alkenoyl taurate where the alkyl contains from about 1 to 4 carbon atoms and the alkenoyl contains from about 10 to about 18 carbon atoms.

When the dioxide compound and the anionic sulfonate surfactant are mixed either beforehand or by addition to the aqueous system. individlually, the resulting mixtures possess a high degree of slimicidal activity which could not have been predicted beforehand from the known activity of the individual ingredients comprising the mixture. Accordingly, it is therefore possible to produce a more effective slime-control agent than has previously been available. Because of the enhanced activity of the mixture, the total quantity of biocide required for an effective treatment may be reduced. In addition, the high degree of biocidal efiectiveness which is provided by each of the ingredients may be exploited without use of the higher concentrations of each. This feature is not only important and advantageous from an economical point of view, but also most desirable from the pollution or ecological standpoints. Specifically, in this regard, it may be pointed out that the smaller the amount of a chemical that is required for effective treatment, the smaller the problem in treating the wastes from these systems. In both cooling water systems and in paper and pulp mill systems, certain discharge of waste water, e.g. blowdown in cooling water systems, is a necessity. However, because of the current concern and legislation regarding the discharge of wastes, the effluent waste water must be treated to reduce and, hopefully, to eliminate any undesirable constituents. This treatment, of course, is time-consuming and costly. Accordingly, a reduction in additive usage will result in a corresponding reduction in costs for the treatment of wastes containing these additives.

To demonstrate the synergism which is obtainable from the combination of the anionic sulfonate surfactant with the 3,3,4,4-tetrachlorotetrahydrothiophenel,l-dioxide (supplied by Diamond Shamrock under designation DS-649), various exemplary anionic sulfonate surfactants were chosen. As earlier indicated, synergistic activity can be obtained by combining the 3,3,- 4,4-tetrachlorotetrahydrothiophencl I -dioxide compound with any anionic sulfonate surfactant which exhibits growth inhibitory or biocidal activity with respect to bacteria, fungi and/or algae. The anionic sulfonate surfactants which were chosen as representative are as follows: sodium linear dodecylbenzene sulfonate (ARCO Chemical Company Ultrawet 35KX) and sodium N-methyl-N-oleoyl taurate (GAF Corporation lngepon T-33).

In order to illustrate the synergistic activity, the efficacy and the comparative effectiveness of the inventive expressed in composi- I SYNERGISTIC INDEX TEST Synergistic activity was demonstrated by adding Compound A and Compound B in varying ratios and over a range of concentrations to liquid nutrient medium which was subsequently inoculated with a standard volume of suspension of the bacterium Aerobacter aerogenes. Following two days incubation, the lowest concentration of each ratio which prevented growth of the bacteria was taken as the end point. Growth or nogrowth was determined by turbidity or clarity, respectively, in the medium. End points for the various mixtures were then compared with end points for the pure active ingredients working alone in concomitantly prepared culture bottles. Synergism was determined by the method described by Kull et al. [F. C. Kull, P. C. Eisman, H. D. Sylwesterowicz and R. L. Mayer, Applied Microbiology, 9, 538-41, (1961)] and the relationships,

(2, (I5 I isadditivity 0,, Q0

I is antagonism I xvasiw where,

TABLE 1 Weight Ratio Quantities Producing End Points (ppm) Q, Q, of A to 8 Q 0,, Mixture 0,, O 0,, Q1,

95/5 2.375 0.l25 2.5 0.95 0.000025 0.95 /50 I 5 L5 3.0 0.60 0.00030 0.60 5/95 I 5 28.5 30.0 0.60 0.0057 0.6I 0/ I 00 0 5000 5000 compositions, various tests were utilized and will be described following.

SPECIFIC EMBODIMENTS EXAMPLE I It is evident from the data recorded in Table I that compositions of the present invention function to control slime growth due to microorganisms not only at equal portions of the respective ingredients, but also where just minor amounts of one or the other are present. This discovery of synergism at the lower levels is extremely valuable since it illustrates conclusively that the ingredients are compatible over the wide percentage by weight range.

BACTERICIDAL EFFECTIVENESS The bactericidal effectiveness of the mixture of Compound A and Compound B of this Example is demonstrated by the following Table in which the inhibiting power of a 50/50 by weight mixture of A and B is TABLEIA Quantity (ppm) required for inhibition Biocidal Material of A. aerogeries Compound A (5%). Compound B (5%). Inert (9071) F UNGICIDAL EFFECTIVENESS In order to test the effectiveness of the inventive mixtures in respect to fungi, evaluations were made following the procedures described by B. F. Shema and J. H. Conkey [.lournal for the Technical Association of the Pulp and Paper Industry, 36, A-30A, (1953)]. The described procedure generally entails incorporating the biocide under test in a nutrient substrate such as agar, malt, etc. and pouring the resulting medium into a Petri dish and allowing the medium to solidify. A button of and B was evaluated together with two recognized fungus inoculum is placed on the surface of the solidified medium and the medium is incubated for a period of 14 days. After the period, the diameterof thecolony .6. SLIME CONTROL EFFECTIVENESS The inventive methods and compositions were also tested with respect to their performance in the control of slime formation in industrial systems. In'this test an industrial recirculating water was obtained from a system which was currently experiencing problems in respect to the fonnation of slime by microorganisms. Such tests do not demonstrate the efficiency of the biocide employed with respect to specific species of microorganisms but instead supply a practical demonstration of the efficacy of the bicoide tested in relation to those communities of microorganisms biocide have evidenced their ability to form slime in actual industrial systems.

In the testing of recirculating water samples, asubstrate evalulation was employed. In such testing identical portions of water samples are treatedwith varying concentrations of biocide and two portions are left untreated to serve as controls. The control portions are plated for total count at the beginning of biocide treatment and all portions are plated for total count at some suitable time period(s) after beginning biocide treatment. Using the counts obtained from plating, the percentage kill (based on the initial count) may be calculated. In this evaluation the water sample was taken from the white water from a cylinder machine system from a paper mill located in the northeastern United States.

For the purposes of comparison, the mixture of A commercial biocides,Pentachlorophenol and the Comia Product described in-T b TABLE 1C Quantity of Percent kill Biocidal Material biocide (ppm) after 6 hours Compound A (57:). Compound B (5%), Inert (90%) 5 80 do. do. do. 10 98 do. do. do. 25 99+ do. do. do. 99+ do. do. I00 99+ Pentachlorophenol (100%) 5 do. l0 17 do. 25 22 do. 50 44 do. I00 76 Commercial Product (l0% active: Dithiocarbamate 5 compound) 10 do. 25 2 do. 50 20 do. I00 21 treatment level which is accomplished this is considered the inhibitoryconcentration. The fungal species utilized as the test microorganism to evaluate the efficacy of the present mixture were Penicillium expansum and aspergillus niger.

TABLE 18 Quantity (ppm) for inhibition Biocidal Material P. expzmsum A. niger Compound A (5%). Compound 8 (50%), lnert (90%) In the foregoing type evaluation, a percentage kill of approximately '70 percent is considered to be most acceptable for industrial purposes. A perusal of the recorded percentages clearly establishes that the composition of the present invention, although less concentrated with respect to active ingredients as compared-to the two commercial products, gave excellent rates of kill even at low treatment levels. As earlier expressed, excellent performance of a biocidal composition at low treatment levels not only provides a most desirable cost perfomiance index, but also provides most desirable advantages from the aspects of pollution abatement, waste treatment costs and the preservation of the ecological strain.

. EXAMPLE 2 SYNERGISTIC COMBINATION:

Compound A: 3,3,4,4-tetrachlorotetrahydrothiophenel l-dioxide Compound B: Sodium N-methyl-N-oleoyl taurate The combinations of this Example contained 3,3,4,4- tetrachlorotetrahydrothiophene-l l-dioxide (hereafter referred to as Compound A) and sodium-N-methyl-N- oleoyl taurate (referred to in this Example as Com- 8 SLIME CONTROL EFFECT lVENESS compared with commercially available products using pound B). As with the previous Example, combinations this test.

TABLE 2C Quantity of Percent kill Biocidal Material biocide (ppm) after 6 hours Compound A (5%), Compound B (5%), Inert (90%) 5 74 do. do. do. 10 98 do. do. do. 25 99+ do. do. do. 50 99+ do. do. 100 99+ Pentachlorophenol (100%) 5 do. l 17 do. 25 22 do. 50 44. do. 100 76 Commercial Product (10% activeSee Table 1C) do. do. 25 2 do. 50 20 do. 100 2l of these ingredients were tested in accordance with the various test procedures outlined in Example 1. The data obtained is recorded in the following Table 2 through 2C.

SYNERGISTIC INDEX TEST For mixtures of Compounds A and B, and for Compound A and Compound B acting alone, the following results were observed:

comprises between 5 to 65% by weight of the synergis- Weight Ratio Quantities Producing End Points Q, Q of A to B Q, 0,, Mixture Q Q Q Q),

The results obtained for this particular combination established unequivocally that the two ingredients behave synergistically together.

BACTERlClDAL EFFECTIVNESS The test procedure as described in Example 1 was utilized. The results established that the composition was effective in controlling this strain of bacteria.

TABLE 2A Quantity (ppm) required for inhibition Biocidal Material of A. Aerogenes Compound A (5%), Compound B (5%),

Inert (90%) 8 FUNGlClDAL EFFECTIVE The fungicidal activity of the composition of this Ex- 60 ample was tested in accordance with the procedure previously described. The results were:

TABLE 2B Quantity (ppm) for inhibition tic combination in admixture with various solvents and solubilizing agents. An example of such a synergistic biocidal product comprises from about 5 to 20% by weight of the anionic sulfonate surfactant, from about 5 to 20% by weight of the 3,3,4,4- tetrachlorotetrahydrothiophene-l l-dioxide and the remainder-composed of such materials as stabilizers, organic solvents, such as alkanols, aromatic hydrocarbons, and/or water.

The foregoing solutions of the biocidal compositions are utilized in order to insure the rapid and uniform dispersibility of the biocides within the industrial water which is treated. It has been found that either aqueous or non-aqueous solvents are generally suitable in the preparation of compositions of the invention, e.g. 7

methyl cellosolve, organic solvents, such as the aliphatic and aromatic hydrocarbons, e.g. kerosene. Based upon the synergism study as outlined above, it was ascertained that in the treatment of paper mill and cooling water, effective biocidal action is obtained when the concentration or treatment level of the combination or admixture of biocides is between 0.5 parts per million to 1,000 parts per million, and preferably between 1 and parts per million, based upon the total content of the aqueous system treated, such as the total quantity of cooling water or paper mill water.

The compositions may also be utilized for the preservation of slurries and emulsions containing carbohydrates, proteins, fats, oils, etc.; dosage levels for the purpose range in the vicinity of 0.5 to The compositions of the invention which can be prepared by merely combining the respective ingredients and mixing thoroughly at standard conditions may be fed continuously to the treated system, e.g. by means of a metered pump, or may be fed periodically at predetermined intervals calculated to control the growth of slime forming organisms in the system. Naturally, in the treatment of cooling water, the feeding of the inventive compositions must be designed to compensate for blowdown in those systems which employ that expedient.

Although the foregoing has been specifically directed to liquid formulations, the combinations of the invention may, of course, be formulated dry with well-known pelletizing agents, e.g. sodium chloride, talc, aluminate, I

ln describing the inventive subject matter, the expression composition has been utilized. However, it is to be understood that physical compositions or combinations are not the sole utility of the invention. If, for example, the separate ingredients of the composition are added independently to a particular system, it is intended that this usage of the subject matter is within the scope of the invention and is to be construed within the broad interpretation of fcomposition and/or combination.

As would be expected, the inventive composition may be added to the cooling water or paper and pulp mill systems at any convenient point. Naturally, in once-through or non-circulating systems, the composition must be added upstream from the point or points at which microorganism control is desired. In circulating systems or pulp and paper systems, the compositions may be added at any point provided that the time lapse and the conditions experienced between point of addition and the point at which the effect of the composition is to be experienced arenot so drastic as to result in the neutralization of the effect of the composition.

Although the invention has been described specifically as being directed to specific compositions comprising 3,3,4,4-tetrachlorotetrahydrothiophenel l dioxide in combination with the anionic sulfonate surfactant as described in Example I and the taurate of Example 2, it is obvious that homologs, analogs, etc. of the 3,3,4,4-tetrachlorotetrahydrothiophenel l dioxide compound certainly are operable for the purpose. Likewise, the derivatives of the specially exemplitied anionic sulfonate surfactants also have utility in the present inventive concept. Moreover, as earlier described, mixtures of the various anionic sulfonate surfactant compounds would also serve the purpose. The provision, of course, is that the surfactant possesses biocidal or growth inhibitory capacity with respect to bacteria, fungi and algae.

It should be noted that while the evidence has been derived from the treatment of samples taken from paper and pulp mill aqueous systems, the compositions and methods of the present invention are broadly applicable to the treatment of aesthetic waters as well as industrial waters such as cooling waters which are 0.5 to 5% by weight of a combination comprising 3,3,4-

- plagued by by organisms, or by the very presence of such organisms.

Having thus described the invention, what we claim l. A method for controllingthe growth of the microorganism Aerobacter aerogenes in an aqueous system in which said microorganism is found which comprises adding to said system so as to contactsaid microorganism an effective amount of a combination comprising 3,3,4,4-tetrachlorotetrahydrothiophenel l -dioxide and a compound selected from the group of alkali metal linear alkylate sulfonate, wherein the alkyl contains from about 10 to 18 carbon atoms, and alkali N- alkyl-N-alkenoyl taurate, wherein the alkyl has from about 1 to 4 carbon atoms and the alkenoyl has from about 16 to 20 carbon atoms and mixtures thereof, wherein the weight ratio of the dioxide to said latter compound is from 5% to to about 95% to 5%.

2. A method according to claim 1 wherein the combination is added to said system in an amount of from about 0.5 to about 1,000 parts by weight of said composition per parts by weight of said aqueous system.

7 3. A method according to claim 1 wherein the compound is sodium linear dodecylbenzene sulfonate.

4. A method according to claim 2 wherein the compound is sodium linear dodecylbenzene sulfonate.

5. A method according to claim 1 wherein the compound is sodiurnN-methyl-N-oleyl taurate.

6. A method according to claim 2 wherein the compound is sodium-N-methyl-N-oleoyl taurate.

7. A method according to claim 2 wherein the composition is added to said system in an amount of l to parts per million parts of said aqueous system.

8. A method according to claim 2 wherein the aqueous system is the aqueous system of a coolingwater system.

9. A method according to claim 2 wherein the system is the aqueous system of a pulp and paper mill system.

10. A method according to claim 8 wherein the composition is added to said system in an amount of l to 100 parts per million and the compound is selected from the group consisting of sodium linear dodecylbenzene sulfonate and sodium-N-methyl-N-oleoyl taurate.

11. A method according to claim 9 wherein the composition is added to said system in an amount of l to 100 parts per million and the compound is selected from the group consisting of sodium linear dodecylbenzene sulfonate and sodium-N-methyl-N-oleoyl taurate.

12. A method for preserving materials which are subject to attack by the microorganism Aerobacter aerogenes which comprises incorporating in said material con taining an amount of said microorganism from about ,4-tetrachlorotetrahydrothiophenel l -dioxide and a compound selected from the group alkali metal linear akylate sulfonate, wherein the alkyl contains from 10 to 18 carbon atoms, and alkali N-alkyl-N-alkenoyl tau rate, wherein the alkyl contains from 1 to 4 carbon atoms and the alkenoyl'contains from about 10 to 16 carbon atoms and mixtures thereof, wherein the weight ratio of the dioxide to said latter compound is from 5% to 95% to about 95% to 5%.

13. A method according to claim 12 wherein the compound is sodium linear dodecylbenzene sulfonate.

14. A method according to claim 12 wherein the compound is sodium-N-methyl-N-oleoyl taurate.

15. A composition which is effective for controlling the growth of the microorganism Aerobacter aerogenes in an aqueous system in which said microorganism is found comprising 3,3,4,4-tetrachlorotetrahydrothiophene-l,l-dixide and a compound selected from the group of alkali metal linear alkylate sulfonate, wherein the alkyl contains from about to 18 carbon atoms and alkali N-alkyl-N-alkenoyl taurate, wherein the alkyl contains from about 1 to 4 carbon atoms and the alkenoyl contains from about 10 to 16 carbon atoms and mixtures thereof, wherein the Weight ratio of the dioxide to said latter compound is from 5% to 95% to about 95% to 5%.

l6. A composition according to claim wherein the compound is; siodium linear dodccylbenzene sulfonate.

17. A com position according to claim 15 wherein the compound is a mixtureof alkali metal linear alkylate sulfonates and the average alkyl size is 12 carbon I atoms.

18. A composition according to claim 15 wherein the compound is sodium-N-methyl-N-oleoyl taurate.

19. A biocidal product which is effective for controlling the growth of the microorganism Aerobacter aer-' ogenes in an aqueous system in which said micoorganism is found comprising from about 5 to by weight of 3,3,4,4-tetrachlorotetrahydrothiophene-l l -dioxide and from about 5 to 20% by weight of a compound selected from the group consisting of alkali metal linear alkylate sulfonate, wherein the alkyl contains from about 10 to 18 carbon atoms and alkali metal N-alkyl- N-alkenoyl taurate, wherein the alkyl contains from about 1 to 4 carbon atoms and the alkenoyl contains from about 10 to 16 carbon atoms and mixtures thereof, and the remainder composed of a material selected from the group consisting of stabilizers, organic and inorganic solvents and mixtures thereof.

20. A biocidal product according to claim 19 wherein the compound is sodium linear dodecylbenzene sulfonate.

21. A biocidal product according to claim 19 wherein the compound is a mixture of alkali metal linear alkylate sulfonates wherein the average size of the alkyl is 12 carbon atoms.

22. A biocidal product according to claim 19 wherein the compound is sodium-N-methyl-N-oleoyl taurate.

23. A method according to claim 1 wherein said weight ratio is 50% to 50%.

24. A composition according to claim 15 wherein said weight ratio is 50% to 50%. 

2. A method according to claim 1 wherein the combination is added to said system in an amount of from about 0.5 to about 1, 000 parts by weight of said composition per parts by weight of said aqueous system.
 3. A method according to claim 1 wherein the compound is sodium linear dodecylbenzene sulfonate.
 4. A method according to claim 2 wherein the compound is sodium linear dodecylbenzene sulfonate.
 5. A method according to claim 1 wherein the compound is sodium N-methyl-N-oleyl taurate.
 6. A method according to claim 2 wherein the compound is sodium-N-methyl-N-oleoyl taurate.
 7. A method according to claim 2 wherein the composition is added to said system in an amount of 1 to 100 parts per million parts of said aqueous system.
 8. A method according to claim 2 wherein the aqueous system is the aqueous system of a cooling water system.
 9. A method according to claim 2 wherein the system is the aqueous system of a pulp and paper mill system.
 10. A method according to claim 8 wherein the composition is added to said system in an amount of 1 to 100 parts per million and the compound is selected from the group consisting of sodium linear dodecylbenzene sulfonate and sodium-N-methyl-N-oleoyl taurate.
 11. A method according to claim 9 wherein the composition is added to said system in an amount of 1 to 100 parts per million and the compound is selected from the group consisting of sodium linear dodecylbenzene sulfonate and sodium-N-methyl-N-oleoyl taurate.
 12. A method for preserving materials which are subject to attack by the microorganism Aerobacter aerogenes which comprises incorporating in said material containing an amount of said microorganism from about 0.5 to 5% by weight of a combination comprising 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a compound selected from the group alkali metal linear akylate sulfonate, wherein the alkyl contains from 10 to 18 carbon atoms, and alkali N-alkyl-N-alkenoyl taurate, wherein the alkyl contains from 1 to 4 carbon atoms and the alkenoyl contains from about 10 to 16 carbon atoms and mixtures thereof, wherein the weight ratio of the dioxide to said latter compound is from 5% to 95% to about 95% to 5%.
 13. A method according to claim 12 wherein the compound is sodium linear dodecylbenzene sulfonate.
 14. A method according to claim 12 wherein the compound is sodium-N-methyl-N-oleoyl taurate.
 15. A composition which is effective for controlling the growth of the microorganism Aerobacter aerogenes in an aqueous system in which said microorganism is found comprising 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a compound selected from the group of alkali metal linear alkylate sulfonate, wherein the alkyl contains from about 10 to 18 carbon atoms and alkali N-alkyl-N-alkenoyl taurate, wherein the alkyl contains from about 1 to 4 carbon atoms and the alkenoyl contains from about 10 to 16 carbon atoms and mixtures thereof, wherein the weight ratio of the dioxide to said latter compound is from 5% to 95% to about 95% to 5%.
 16. A composition according to claim 15 wherein the compound is sodium linear dodecylbenzene sulfonate.
 17. A composition according to claim 15 wherein the compound is a mixture of alkali metal linear alkylate sulfonates and the average alkyl size is 12 carbon atoms.
 18. A composition according to claim 15 wherein the compound is sodium-N-methyl-N-oleoyl taurate.
 19. A biocidal product which is effective for controlling the growth of the microorganism Aerobacter aerogenes in an aqueous system in which said micoorganism is found comprising from about 5 to 20% by weight of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and from about 5 to 20% by weight of a compound selected from the group consisting of alkali metal linear alkylate sulfonate, wherein the alkyl contains from about 10 to 18 carbon atoms and alkali metal N-alkyl-N-alkenoyl taurate, wherein the alkyl contains from about 1 to 4 carbon atoms and the alkenoyl contains from about 10 to 16 carbon atoms and mixtures thereof, and the remainder composed of a material selected from the group consisting of stabilizers, organic and inorganic solvents and mixtures thereof.
 20. A biocidal product according to claim 19 wherein the compound is sodium linear dodecylbenzene sulfonate.
 21. A biocidal product according to claim 19 wherein the compound is a mixture of alkali metal linear alkylate sulfonates wherein the average size of the alkyl is 12 carbon atoms.
 22. A biocidal product according to claim 19 wherein the compound is sodium-N-methyl-N-oleoyl taurate.
 23. A method according to claim 1 wherein said weight ratio is 50% to 50%.
 24. A composition according to claim 15 wherein said weight ratio is 50% to 50%. 